Trisazo dyestuffs



Patented Mar. 9, 1954 TRISAZO DYESTUFFS Walter Hanlxart, Riehen, Switzerland, assignor to Cilia Limited, Basel, Switzerland, a Swiss No Drawing. Application June 11, 1951, Serial No. 231,058

Claims priority, application Switzerland June 22, 1950 11 Claims. 1

According to this invention valuable new trisazo-dyestuil's are made by coupling a diazodisazo-compound of an amine oi. the general formula R1 represents a heterocyclic radical containing a 5-membered heterocyciic-ring, which contains at least two hetero-atoms of which at least one is a nitrogen atom bound exclusively in the ring,

R2 represents the radical of a middle component of the benzene or naphthalene series, advantageously one which contains bound in a position vicinal to the azo group connecting R: and R0 a group capable of taking part in the formation of metal complexes, and

R3 represents the radical of a 5-hydroxynaphthalene-7-sulfonic acid bound in the 6-position to the azo group and which is bound in at least one of the positions 1 and 2 directly or advantageously through a bridge member to the diazotizable NH: group,

with an azo component which is itself capable of forming complex metal compounds.

The amino-disazo-dyestufl's of the above for- Inula can be made by coupling a diazo compound of an amine of the formula Rl-NHI with a middie component of the constitution HReNI-h. further diazotizing the resulting amino-monoazodyestuil', and coupling the diam compound in an alkaline medium with a compound of the formula HR1NH2. In the foregoing formulae R1, Ru

and R1 have the meanings given in the preced- 3 ing paragraph.

The initial component of the formula Ri-NH: serving as starting material contains a 5-membered heterocyclic ring, to which the -NH: group may be bound directly; the latter group may also be bound to an aromatic ring, for example, a benzene ring, which is either linked to the said heterocyclic ring by a simple direct bond or fused thereto (that is to say, in the latter case two carbon atoms of the aromatic ring also form part of the heterocyclic ring). The heterocyclic ring contains at least two heteroatoms of which at least one is a nitrogen atom bound exclusively in the ring, thus a nitrogen atom of which all the three valencies are saturated in forming the ring. The manufacture of the dyestufis of the present invention is in other respects facilitated by starting from initial components which are free from hydroxyl groups imparting coupling properties thereto.

Iill

Valuable results are obtained, for example. with initial components of the formula RINH2, in which the amino group is bound to a benzene ring of which two vicinal ring carbon atoms also form part of a 5-membered heterocyclic ring containing at least two nitrogen atoms, and at least one of which nitrogen atoms is bound exclusively in the ring.

The initial components may contain in addition to the hetero-ring and the benzene ring fused thereto at the most one further benzene ring which may be fused to the first mentioned benzene ring (thus forming a naphthalene ring) or which may be linked directly by a single bond to the hetero ring.

As examples of suitable initial components the following compounds may be mentioned:

NH B-amino-indasole N 6-amlno-benzimidasole 2-methyl-B-amino-bensimidazole T-amino-bensimidalole 4- or 'I-amino-benztriasole G-emino-benztrlarole N H ll G-amino-benzthiazole and also the compounds of the formulae (subsequently eulfonated, the position or the eulfonic acid group being uncertain) The amines or the formula HR'.-NH2 serving as middle components tor making the aminodisazo dyestufls of the foregoing formula may belong, for example, to the naphthalene or advantageously the benzene series. The substituent which is capable of taking part in the formation 0! metal complexes, may, for example, be a hydroxyl group, a carboxylic acid group, an --OCH:COOH group or more especially an alkoxy group; as alkoxy groups there are especially suitable ethoxy groups and above all methoxy groups. As middle components there come into consideration, for example, the followin compounds:

Amlnobenzene,

l-amino-a-methylbenzene,

1-aminonapthalene,

l-amino-z-methoxynaphthalene,

l-amino-2-methoxynaphthalene-B- or 7-suli'onic acid.

l-amino-2-carboxymethoxy-naphthalene.

l-amino-z-methoxyor -2-ethoxybenzene,

1-amino-2-methoxyor -2-ethoxy-5-methylben- $8110, 1-amino-2z5-dlmethoxyor -2:5-dlethoxybensens,

4 l-aminmz-ethoxy-5-methoxybenzene. 1-amino-2-methoxy-5-ethoxybenzene, 1-amlno-2-propyioxy-S-methoxyhenzene, l-amino-2-carboxymethoxy-5-methylbenzene, 1-amino-2-hydroxy-5-methylbenzene, l-acetylamino 2 hydroxy'benzene (the acetyl group being split oi! alter coupling).

The azo-components of the formula E-R:NH:

are naphthalene derivatives which contain in the 5-position a l vdroxyl group, in the 7-position a suli'onic acid group. and the diazotizable -NH: group bound either directly to the naphthalene nucleus in the 1- or 2-poeition or bound in at least one of the positions 1 and 2 by means or a bridge member. There may be used for example two-components of the Iormula Hols wherein one x stands for a hydrogen atom and the other X stands for an NH:-group or one of the radicals sou:

furthermore 2-amino-5-hydroxynaphthalene-7 sulionie acids containing a substituent in l-position and also those derivatives 0! 2-amino-5-hY- droxynaphthalene 7 sulionic acid which are bound to the diazotlzable NH: group both in the 2-position and in the 1-position oi the naphthalene nucleus that is to say bound by means oi a ring iused to the naphthalene nucleus.

As compounds of the formula HR=NH: which are suitable for the present process the following may be mentioned:

and

. 2-(f-aminobenzoyl) amino-5-hydroxynaphthalene-I-sulionic acid, 1- (4-aminobenzoyl) amino-5-hydroxynaphthalene-7-sullonie acid.

the asymmetrical urea derivative of the formula NH-C -N BONED and also those 01 the iormulae |i HOzS- -N NH:

and

N: Q H013 NE NH:

Especially valuable is 2-(4'-aminophenyl) amino- 5 -hydroxynaphthalene 1:3 disulfonic acid 01' the formula H013 NH NH:

SOJH

In making the amino-disazo-dyestuffs of the formula R1-N=NR2N=NR3-NH2 in the manner described above, the coupling of the diazo can he carried out by methods in themselves known, for example, by means of hydrochloric acid and sodium nitrite. The resulting diazomonoazo-compound is coupled with an azo-component of the constitution HR3NH2 in an alkaline medium, for example, a medium rendered alkaline with an alkali carbonate.

In accordance with the process of the invention the diazo-disazo-compounds of the formula first mentioned above are coupled with azo-components which are themselves capable of forming complex metal compounds. For this purpose there come into consideration, for example, compounds which contain a salicylic acid grouping, providedthat they are still capable of coupling with the particular diazo-disazo-ccmpound used. l-hydroxybenzene-2-carboxylic acid itself and substitution products thereof capable of coupling. such as 6-chloroor B-methyl-l-hydroxybenzene-Z-carboxylic acid, can be coupled only with some of the diazo-disazo compounds used in the present process, advantageously those which contain in a position vicinal to the diazotized amino group no substituents rendering coupling difllcult such as sulfonic acid groups.

Especially valuable azo components in this connection are 8-hydroxyquinolines, such, for example, as 8-hydroxyquinoline-7-sulfonic acid and above all ii-hydroxyquinoline itself.

The amino-disazo dyestuffs are advantageously diazotized by the so-called indirect method in which, for example, a solution or suspension which contains the amino-disazo-dyestuff in the form or an alkali salt and advantageously a slight excess oi. tree alkali together with the necessary quantity of nitrite. is coupled in the presence of an excess of dilute hydrochloric acid.

The coupling of the amino-disazo-compound with th azo-components of the above kind is conducted with advantage in an alkaline medium, for example. a medium rendered alkaline with an alkali carbonate or an alkaline earth metal hydroxide, if desired with the addition of a substance favoring coupling, such as pyridine.

In general it is desirable so to select the starting materials that in all two sultonic acid groups are present in the trisazo-dyestuil.

The new trisazo-dyestufls oi the invention correspond to the general formula R1 represents a heterocyclic radical containing a 5-membered hetero-ring, which contains at least two hetero-atoms of which at least one is a nitrogen atom bound exclusively in the ring.

R2 represents the radical of a middle component of the benzene or naphthalene series, advantageously one which contains in a position vicinal to the azo group connecting R2 and R: a group capable of taking part in the formation of metal complexes.

R3 represents the radical of a 5-hydroxynaphthalene-T-sulfonic acid bound in the 6-position to the azo-group connecting R2 and Rs, and which radical is bound in at least one of the positions 1 and 2 directly or advantageously by means of a bridge member to the azo group connecting R3 and R4, and

R4 represents the radical of an azo-component which is itself capable of forming metal complexes.

The dyestufls of this invention are suitable for dyeing a very wide variety of materials, for example, animal fibers such as wool, silk and leather, and especially for dyeing or printing cellulose materials such as cotton, linen and artificial silk and staple fibers of regenerated cellulose. The dyestuffs are advantageously treated on the fiber or partially on the fiber and partially in the dyebath with agents yielding metal by known methods. It is of advantage, for example, to use the process of U. S. Patent No. 2,148,659, in which first the dyeing and then the treatment with an agent yielding metal are carried out in the same bath. As agents yielding metal there come into consideration more especiaily those which are stable towards alkaline solutions, such as complex copper tartrates and the like.

In some cases especially valuable dyeings are produced by working according to the process in which a dyeing or print produced with the metalfree dyestvif is after-treated with an aqueous solution containing a basic formaldehyde con densation product from a compound containing in the molecule at least once the atorr rouping for example, dicyandiamide or dicyandiamidine. or a compound easily convertible into such a compound, for example, cyanamide, and which solution also contains a water-soluble, especially complex copper compound. Such processes are described, for example, in British Patent No. 619.969.

The following examples illustrate the invention, the parts and percentages being by weight:

Example 1 13.3 parts of G-amino-indazole are dissolved in 300 parts of cold water and 45 parts of hydrochloric acid of 30 per cent strength, and after N/CEO H? the addition of some ice diazotization is carried out by pouring in a solution of 1.6 parts of sodium nitrite in 35 parts of water. A small quantity of sulfaminic acid is added until the nitrite reaction disappears, and then coupling is carried out in a manner in itself known with 13.7 parts of l-amino-2-methoxy-5-methylbenzene in an acetic acid medium while cooling with ice. When the coupling is finished, suflicient hydrochloric acid is added to produce an acid reaction to Congo, the completely precipitated monoazodyestufl is separated by filtration, and the latter is then stirred in a mixture of 1000 parts of water and 108 parts of sulfuric acid of 95 per cent strength and diazotized at 20 C. by the rapid addition of 10 parts of sodium nitrite in the form of a solution of 20 per cent strength. After 5-10 minutes the diazotization is finished, and the diazo monoazo-compound is completely dissolved. Coupling with 41 parts of 2-(4'- aminophenyl) amino 5 hydroxynaphthalene- 7 3'-disulfonic acid is then carried out while cooling with ice in a solution rendered alkaline with sodium carbonate. When the coupling is finished, the precipitated disazo-dyestuff is separated by filtration and washed on the filter with sodium chloride solution of 10 per cent strength until the coupling component can no longer be detected. The resulting disazo-dyestufi is dissolved in the warm in 1500 parts of water and 13.5 parts of sodium hydroxide solution of 30 per cent strength. the whole is cooled by the addition of ice to about 10 C., then mixed with '1 parts of sodium nitrite in the form of a solution of per cent strength and diazotization is carried out by pouring in 58 parts of hydrochloric acid of 30 per cent strength which has been diluted with 150 parts of water. The dlazo solution is stirred for a few hours while cooling with ice, the excess of nitrite is decomposed by means of suliaminic acid, and there is added first a weakly hydrochloric acid solution of 14.5 parts of 8-hydroxyquinoline and then a solution of 60 Darts of sodium carbonate in 250 parts of water. When the coupling is finished, the precipitated dyestuii which in its free acid state corresponds to the formula 8 the single bath or 2-bath after-coppering process navy blue tints which are fast to washing and light.

By using instead of the first coupling component a corresponding quantity of 1-amino-2- carboxy-methoxy-5-methylbenzene, there is obtained a similar dyestuff which dyes somewhat more greenish tints. In its i'reeacid state this dyestui'f corresponds to the formula By using 1-amino-2 zfi-dimethoxybenzene the tint is shifted still further towards green, whereas l-amino-3-methyl-benzene yields a dyestufl producing violet tints. By using as the initial component 5-amino-indazole, and otherwise working in accordance with the above example, a practically identical dyestuil is obtained. All the dyes are distinguished by their very good fastness to washing.

Example 2 14.7 parts of z-methyl-c-amino-benzimidaaole are dissolved in 100 parts of water and 25 parts of hydrochloric acid of 30 per cent strength, and after the addition of some ice diasotization is brought about by the rapid addition of 35 parts of a sodium nitrite solution of 20 per cent strength. The whole is stirred for a short time whilee cooling, any excess of nitrite is decomposed by means of sulfaminic acid, and coupling is carried out in known manner by means of a hydrochloric acid solution of 13.! parts of 1- amino-2-methoxy-5-methylbenzene, the free hydrochloric acid being neutralized with sodium acetate. When the coupling is finished, the monoazo-dyestuil is separated by filtration and washed with a sodium chloride solution of 5 per cent strength acidified with a small quantity of hydrochloric acid, and then suspended in 350 parts of cold water. 22 parts of sodium hydroxide solution of 30 per cent strength are first added. and then 35 parts of a sodium nitrite solution of 20 per cent strength and some ice are added, and diazotization is brought about by pouring in 58 parts oi hydrochloric acid of 30 per cent strength. The diazotization finishes very rapidly and the diazo-monoazo-compound is completely dissolved. The latter is coupled, while cooling with ice, with a solution of 41 parts of 2-(4'- aminophenyl) amino 5 hydroxynaphthalene- 7:3'-disulfonic acid rendered alkaline with sodium carbonate. When the coupling is finished sodium chloride is added to complete the pre cipitation, the disazo-dyestufi is separated by liltration and washed on the filter with sodium chloride solution of 15 per cent strength until the coupling component can no longer be detected.

on sac no NHQN=N-j -on N\ pvN=N-qN=jw on: N

is separated by filtration and dried. It is a black powder which dissolvesin concentrated sulfuric acid with a green-blue coloration and in water The dyestufl is then dissolved in 1000 parts of warm water with the addition of 20 parts of sodium hydroxide solution of 30 per cent strength.

with a blue-violet coloration, and dyes cotton by and after the addition of ice and 35 parts of a sodium nitrite solution 01' 20 per cent strength diazotization is brought about by pouring in 58 parts of hydrochloric acid of 30 per cent strength. The whole is stirred for a short time while cooling, any nitrite still present is decomposed with suliaminic acid, a hydrochloric acid solution of 14.5 parts of .hydroxyquinoline is added and then 80 parts of sodium carbonate dissolved in 250 parts of water are then added. The resulting trisazodyestuil is separated by filtration and dried. It is a black powder which dissolves in concentrated sulfuric acid with a blackish blue coloration and in water with a blue coloration, and dyes cotton by the single bath or 2-bath after-coppering process fast navy blue tints.

Very similar dyestuiis are obtained by using, instead of 2-methyl-6-aminobenzimidazole, 6- aminoor 'l-amino-benzimidazole. A dyestufi yielding blackish navy blue tints is obtained by using 6-aminobenzimida:.:ole as the initial component and 1-amino-2-hydroxy-5-methylbenzene as the first coupling component. By using the amino-naphthoimidazole of the formula Nil C-CH:

as initial component, there is obtained a dyestufi' yielding greenish navy blue tints.

A valuable dyestuif yielding on cotton blackish navy blue tints when after-coppered is obtained by coupling diazotized 2-methyl-6-amino-benzimidazoie with l-amino-2-hydroxy-5-methylbenzene, diazotizing the amino-monoazo dyestuff and coupling it with 2-(4'-aminophenyl) -amino- -hydroxynaphthalene-7,3-sulfonic acid, diazotizing again the so obtained product and coupling it with S-hydroxyquinoline. This dyestuff corresponds in its free acid state to the formula 10 amino-2-methoxy-5-methylbenzene is carried out, the hydrochloric acid being neutralized with sodium acetate. Coupling finishes in a few hours. The monoazo-dyestutf is separated by filtration, dissolved in 1000 parts of cold water and 33 parts of sodium hydroxide solution of 30 per cent strength, then mixed with 36 parts of sodiumnitrite solution of 20 per cent strength, and diazotization eflected at about 15 C. by pouring in #6 parts of hydrochloric acid of 30 per cent strength diluted with 100 parts of water. Diazotization takes place very rapidly, and at first a clear solution is obtained and .then a sandy precipitate. After stirring for about one hour, coupling is e1- fected with a solution of 41 parts of 2-(4'-aminophenyl) amino 5 hydroxynaphthalene 7 :3- disulionic acid containing an excess of sodium carbonate or sodium bicarbonate, while cooling with ice. When the coupling is finished, the whole is heated to about 70 C., the dyestufi is precipitated by the addition of 15 parts of sodium chloride for every 100 parts of coupling mixture, and the product is separated by filtration at about 30-35 C., that is to say, when the runnings from the filter paper have become almost colorless. The filter residue is washed with sodium chloride solution of 15 per cent strength until all the excess of coupling component has been removed. The disazo-dyestuff is dissolved at C. in 2000 parts oi water with the addition of 13 parts of sodium hydroxide solution of 30 per cent strength. .The whole is allowed to cool, 35 parts of sodium nitrite solution of 20 per cent strength are added together with a suilicient quantity of ice to produce a temperature of about 10 C. Diazotization is then carried out by pouring in parts of hydrochloric acid of 30 per cent strength which has been diluted with 100 parts of water. The whole is stirred for a few hours while cooling, the excess of nitrite is decomposed, and there are added first a hydrochloric acid solution of 14.5 parts of B-hydroxyquinoline and then parts of sodium carbonate dissolved in 240 parts 0! HC C/ mo Hols NHQN=N on \Q ran-Quay OIH N Example 3 13.4 parts of 6-amino-benztriazole are dissolved in parts of water with the addition of 45 parts of hydrochloric acid of 30 per cent strength. To is separated by filtration and dried.

Some ice is added and diazotization is carried out by pouring in 35 parts of sodium nitrite solution 01' 20 per cent strength. When any excess 01 nitrite has been decomposed, coupling with a water. When the coupling is finished the precipitated dyestufi' which in its free acid state corresponds to the formula It is a blackish powder which dissolves in concentrated sulfuric acid with a green-blue coloration and in water with a blue-violet coloration. It dyes cotton when aiter-coppered navy blue tints which hydrochloric acid solution of 13.? parts of 1- 75 are very fast to washing.

Inl il component gfigflfi Second coupling component End component 55323 32 OCH: IQddilh 115W blue.

N NE: Qua. nmmNnO-smn N NE, E soin N 8 note NHGNH:

blackish navy blue. OH

N OCH: BOaH black-blue. OH

NE: NE NH, NH: N

GH-N 0 CH; BOIH navy blue.

0H 1 0-H! NH now NE NH: --N N nooc-c-N OCH; sou: Do.

2 on C-NH:

NH: Hols NH- -Nn, N N

The first dyestufl oi the above table corresponds carried out with a hydrochloric acid solution of to the formula 13.! parts of 1-a.mino-2-methoxy-5-methy1ben N mo HOaB N==N on N N=NQ N=N N C Ha HA The dyestufl' obtainable from G-amino-benztrizene, the hydrochloric acid being neutralized with azole as initial component, 1-amino-2:5-dimeth- 55 sodium acetate. The monoazo-dyestufl is sepaoxybenzene as first coupling component, 2-(4'- rated by filtration and washed with a dilute aminophenyl) amino 5 hydroxynaphthalenesodium chloride solution acidified with a small 7:3'-disulfonic acid as second coupling compoquantity of hydrochloric acid. The dyestufl is nent, and B-hydroxyquinoline as and component stirred in 1000 parts of water and mixed with (8th dyestufl of the table) corresponds to the no 26 parts of sodium hydroxide solution of 30 per formula cent strength. To the yellow dyestufl suspension N BIC-0 Hots NHQN=N --on N Highs 0... N

-CH: H

Example 4 are added 7.5 parts of sodium nitrite dissolved 15 parts of fi-amino-benzthiazole are dissolved in water and then at Main? temperature in 400 parts 01 water and 58 parts of hydrochloric parts of hydrochloric acid of 30 per cent strength acid of 30 per cent strength. and the whole is diluted with about Parts Of t The cooled with ice to 0 (1-. and diazotized with 7 d m-a p u d.w porar ly d ss lves parts of sodium nitrite in the form of a. solution to give a clear solution, is stirred for a short time of about 20 per cent strength. Coupling is then 78 and then coupled with 41 parts of 2-(4'-aminophenyl) amino hydroxynaphthalene 7:3- disulfonic acid in a medium rendered alkaline with sodium carbonate or sodium bicarbonate. When the coupling is finished, the disazo-dyestufl. is separated by filtration, washed with a dilute sodium chloride solution and dissolved in 3000 parts of hot water. When the solution has cooled to about 30 C.. it is further cooled by the addition of ice to -15 C.. 7 parts of sodium nitrite are added in the form 01' a solution or per cent strength, and then 58 parts of hydrochloric acid or per cent strength diluted with 150 parts of water are added. The diazo compound is stirred for a few hours, the excess of nitrite is decomposed, 14.5 parts of B-hydroxyquinoline are added in solution in hydrochloric acid and then a solution of 75 parts of sodium carbonate in 240 parts of water is added. When the coupling is finished the trisaao-dyestuil' is separated by filtration, and dried. It is a blackish powder which dissolves in concentrated sulfuric acid with a blackish coloration and in water with a blue coloration, and dyes cotton when ai'ter-coppered reddish navy blue tints.

By using instead of fi-aminobenzthiazole, a corresponding quantity of 2-aminothiazole there is obtained a dyestufl yielding somewhat greener tints.

Example 5 100 parts of cotton are entered at 50 C. into a dyebath containing in 4000 parts of water 1.5 parts of the dyestufl obtainable as described in the first paragraph of Example 1 and 2 parts of anhydrous sodium carbonate. The temperature is raised in the course of 20 minutes to 90 95 C.. parts of crystalline sodium suliate are added, and dyeing is carried on for 30 minutes at 90-100 C. The whole is then allowed to cool to about 70 C.., 3 parts of complex sodium copper tartrate of approximately neutral reaction are added, coppering is carried out for V hour at about 80 0., and the dyeing is then rinsed with cold water. If desired, the dyeing may be soaped by after-treatment with a solution containing 5 parts of soap and 2 parts of anhydrous sodium carbonate in 1000 parts of water. A navy blue dyeing of good iastness to washing and light is obtained.

what is claimed is:

l. A trisazo dyestufl corresponding to the formula in which R1 represents a heterocyclic radical containing a S-membered hetero-ring selected from the group consisting of indazole, imidazole, trlazole and thiazole rings, R2 represents the radical of a middle component free from sulfonic acid groups and selected from the middle components of the benzene and naphthalene series, Rs represents the radical 01 a 5-hydroxynaphthalene-T-sulfonic acid bound in the 6-position to the azo-group connecting R: and R3, and which HIC radical is bound in at least one of the positions 1 and 2 to the azo group connecting Ba and R4, and R4 represents a member selected from the group consisting of the radical of an 8-hydroxyquinoline and the radical of a hydroxybenzene ortho-carboxylic acid.

2. A trisazo dyestufl corresponding to the iormula in which R1 represents a benzene radical of which two vicinal ring carbon atoms also form part of a triazole ring, R2 represents a benzene radical i'ree irom sulfonic acid groups and containing the azo groups in para-position and containing in ortho-position to the azo group connecting Rd and Rs a group which is capable of taking part in the formation of metal complexes, R3 represents the radical of a 5-hydroxynaphthalene-l-sulionic acid bound in the 6-position to the azo-group connecting Re and Ba. and which radical is bound in at least one o! the positions 1 and 2 to the azo group connecting R: and R4, and R4 represents the radical 0! an 8- hydroxyquinoline.

3. A trisazo dyestufl. containing two sulionic acid groups and corresponding to the formula in which R1 represents a benzene radical of which two vicinal ring carbon atoms also form part or a triazole ring, R2 represents a benzene radical free from sulionic acid groups and containing the azo groups in para-position and containing in ortho-position to the azo group connecting R2 and the naphthalene nucleus a group which is capable of taking part in the formation of metal complexes and R4 represents the radical of an B-hydroxyquinoline bound to the azo group in 5-position.

4. A trisazo-dyestufl containing two sulionic acid groups and corresponding to the formula R -N=N-R:N=N

in which R1 represents a benzene radical of which two vicinal ring carbon atoms also form part of a triazole ring, R2 represents a benzene radical containing the azo groups in para-position and containing in ortho-position to the azo group connecting R2 and the naphthalene nucleus a group which is capable of taking part in the formation or metal complexes and R4 represents the radical 01' an B-hydroxyquinoline bound to the azo group in 5-position.

5. The trisazo dyestuil' o! the formula 17 6. The trieazo dyeatuif of the formula 7. The trisazo dyestuif of the formula 8. The trisazo dyestuff of the formula 9. The triaazo dyestufl of the formula 10. A trisazo dyeetuff corresponding to the formula in which R1 represents an indalole radical, R2 represents a benzene radical containing the aao groups in para-position and containing in orthopoeition to the are group connecting Re and the naphthalene nucleus a group which is capable of taking part in the formation of metal complexee and R4 represents the radical of an 8- hydroxyquinoline bound to the are group in position.

11. A trieazo dyeetuif corresponding to the formula No references cited. 

1. A TRISAZO DYESTUFF CORRESPONSING TO THE FORMULA 